Benzoxanthene and benzothioxanthene dyestuffs

ABSTRACT

wherein X is oxygen or sulfur, R1 is hydrogen, alkyl having 1 to 20 carbon atoms, methoxycarbonylmethyl, ethoxycarbonylmethyl, lower alkoxycarbonyl or phenyl, R2 is alkoxycarbonyl having 1 to 20 carbon atoms, lower acyl or benzoyl, cyano, carbonamido or phenylcarbonamido, R3 and R4 represent simultaneously hydrogen or lower alkoxy or R3 is lower alkoxy and R4 is hydrogen, R5 and R6 are hydrogen or halogen atoms, lower alkyl, alkoxy or alkoxycarbonyl. These dyestuffs yield brilliant yellow to red dyeings in synthetic polymers especially in polyethylene terephthalate with an intense yellow green to orange fluorescence. Due to their high fluorescence they can also be used for preparing daylight fluorescent pigments.   Dyestuffs consisting of the mixture of isomers of the formula I

United States Patent [191 Troster [451 Dec. 10, 1974 [75] Inventor: Helmut Troster, Frankfurt am Main,

Germany [73] Assignee: Hoechst Aktiengesellschaft,

Frankfurt am Main, Germany [22] Filed: Aug. 2, 1973 [21] Appl. No.: 384,785

[30] Foreign Application Priority Data Aug. 4, 1972 Germany 2238330 [52] US. Cl. 260/287 R, 8/54.2, 8/178 R, 8/179, 252/3012 R, 260/37 P, 260/40 R, 260/288 R [51] Int. Cl....- C07d 35/32 [58] Field of Search 260/287 R, 288 R [5 6] References Cited UNITED STATES PATENTS 3,376,303 4/1968 Fuchs et al. 260/288 Primary ExaminerG. Thomas Todd Attorney, Agent, or FirmCurtis, Morris & Safford [57] ABSTRACT Dyestuffs consisting of the mixture of isomers of the formula I a nd M mar l 2 wherein X is oxygen or sulfur, R is hydrogen, alkyl having 1 to 20 carbon atoms, methoxycarbonylmethyl, ethoxycarbonylmethyl, lower alkoxycarbonyl or phenyl, R is alkoxycarbonyl having 1 to 20 carbon atoms, lower acy] or benzoyl, cyano, carbonamido or phenylcarbonamido, R and R represent simultaneously hydrogen or lower alkoxy or R is lower alkoxy and R is hydrogen, R and R are hydrogen or halogen atoms, lower alkyl, alkoxy or alkoxycarbonyl. These dyestuffs yield brilliant yellow to red dyeings in synthetic polymers especially in polyethylene terephthalate with an intense yellow green to orange fluorescence. Due to their high fluorescencethey can also be used for preparing daylight fluorescent pigments.

8 Claims, No Drawings BENZOXANTI-IENE AND BENZOTHIOXANTHENE in the presence of acidic condensation agents into a hy- DYESTUFFS drazone of the formula IV The present invention relates to novel valuable dyestuffs consisting of the mixture of isomers of the formula I ll d whereby in the formulae II, III and IV the substituents R1 R R R R and R as well as X have the above: meanings and this hydrazone 1s cyclized m the presence H H of basic condensation agents. XI/N To prepare the dyestuffs the starting compound II is RP reacted with at least equivalent amounts of the methyleneactive component III in the presence of about O 0.0lto 0.1 mol of an acidic condensation agent per mol of the starting compound at an elevated temperature.

I Condensation can be effected either in a suitable or- R; (I) ganic solvent such as for example isobutanol, monomethylglycol, chlorobenzene, dichlorobenzene, nitrobenzene, dimethyl forr'namide, N-methyl-pyrrolidone, acetic acid or, with an excess of the compound III at a, temperature of from about 100C to about 200C, if desired under pressure. The reaction time is between about 30 minutes and 8 hours. In some cases it is suitable to remove the reaction water and other easily volatile by-products from the reaction mixture by distillation or by passing thru an inert gas stream.

After cooling the hydrazone formed can be isolated in usual manner. As acidic condensation agents can be considered aromatic sulfonic acids such as benzeneor toluene-sulfonic acid, alkane-sulfonic acids such as ethane-sulfonic acid, amidosulfonic acid, mineral acids as for example sulfuric or phosphoric acid or gaseous hydrogen chloride. When using protic solvents such as acetic or propionic acid these ones already act as acidic condensation agents. I

Examples for compounds of the formula III are acetoacetic acid methyl ester, acetoacetic acid butyl, -isopropyl-, -dodecyl-, -2- ethoxy-ethylesters, butyryl- U acetic acid ethyl ester, 'y-diethylacetoacetic acid ethyl ll ester, stearoyl-acetic acid ethyl ester, phenylacetoa- 0 NH" cetic acid ethyl ester, benzoyl and 4-methoxybenwherein X is oxygen or sulfur, R is hydrogen, alkyl having 1 to 20 carbon atoms, methoxycarbonylmethyl, ethoxycarbonylmethyl, lower alkoxycarbonyl or phenyl, R is alkoxycarbonyl having 1 to 20 carbon atoms, lower acyl or benzoyl, cyano, carbonamido or phenylcarbonamido, R and R represent simultaneously hydrogen or lower alkoxy or R is lower alkoxy and R is hydrogen, R and R are hydrogen or halogen atoms, 40 lower alkyl, alkoxy or alkoxycarbonyl, as well as to a process for preparing these dyestuffs.

Preferred compounds are those of the formula I, wherein R is lower alkyl, R is alkoxycarbonyl having 1 to 20 carbon atoms, R and R are hydrogen or lower alkoxy and X, R and R have the above meaning.

The novel dyestuffs are obtained if a benzoxanthene or benzothioxanthene-dicarboxylic acid hydrazide of the formula II 5 5 zoylacetic 4-methoxybenzoylacetic acid ethyl ester, ox-

"-" alylacetic acid diethyl ester, acetyl-acetone, benzoylacetone, y-dimethylacetylacetone, dibenzoylmethane y-ethoxyacetylacetone, acetyland benzoylpyruvic acid ethyl ester, acetonedicarboxylic acid dimethyl ester, benzoylacetonitrile, formylacetophenone, acetoa- [I cetic acid amide, acetoacetic acid methyland diethylamide, acetoacetic acid anilide, -p-anisidide, -3-

chloroanilide, -5-chlor0-2-toluidide, -o-toluidide, -cyis converted with a compound of the formula III clohexylamide, -octyla.mide, 2,4-dichlorobenzoylacetic acid.

R1 COCH2 R2 The ring closure of the hydrazone to form the dye- (Ill) stuff is expediently carried out in an organic solvent such as butanol, isobutanol, pyridine, dimethyl sulfoxide, suitably in acid dialkyl amides, as for example dimethyl formamide, formamide, dimethyl acetamide, hexamethyl-phosphoric acid triamide or N-methylpyrrolidone in the presence of an alkaline compound such as sodium or potassium acetate, potassium carbonate or hydroxide, piperidine, morpholine or triethyl amine at temperatures of from about 80 to about 180C, if desired under pressure.

If the hydrazone has already been prepared in an organic solvent of the above-mentioned type, it may be cyclized without previous isolation directly in the reaction mixture after neutralizing the acidic condensation agent by addition of one of the bases mentioned. The dyestuff crystallized can be separated in usual manner.

The benzoxanthene and benzothioxanthenedicarboxylic acid hydrazides of the formula 11 used as starting compounds are known from German Patent Specification No. 1,297,259, US. Pat. No. 3,357,985,

British Patent Specification No. 1,245,478 and German Offenlegungsschrift No. 2,008,491.

The novel dyestuffs obtained according to the invention are very suitable for dyeing synthetic materials such as acetyl cellulose, polyamides and especially polyethyleneglycol-terephthalate. Brilliant yellow to red dyeings were obtained having not only a good fastness to light but also an excellent fastness to sublimation. Due to their high fluorescence the products of the invention are very suitable for preparing daylight fluorescent pigments. They may also be used as fluorescent dyestuffs for dyeing synthetic polymers such as polystyrene, polymethacrylate and polyvinyl chloride. They yield in these materials yellow to red shades, which have an intense yellow green to orange fluorescence and are distinguished by a high resistance toheat and to light. Another field of application is the dyeing of synthetic fibreforming polymers such as polyethyleneglycol terephthalate in the mass.

Furthermore a big part of the products of the invention is very suitable for dyeing synthetic materials from organic solvents such as perchloroethylene.

The following Examples illustrate the invention.

EXAMPLE-1 a. 20.0 Grams of benzothioxanthene-3,4- dicarboxylic acid hydrazide and 0.5 g oftoluenesulfonic acid were stirred for 1 hour at 135-140C in 120 g of acetoacetic acid ethyl ester, while'passing thru a weak nitrogen stream. After cooling the reaction mixture was diluted with 140 ml of methano], the orange hydrazone formed was suctionflltered, washed with methanol and dried.

b. A mixture of 1 1.0 g of the hydrazone obtained according to a), 110 ml of dimethyl formamide and 0.1 1 g of anhydrous potassium acetate was heated for 30 minutes to the boiling point. After cooling the crystallized red mixture of dyestuff isomers of the formula was suction-filtered, washed with methanol and water and dried. The compound recrystallized from dimethyl formamide yielded the following values Calc: C

72 H Found: C 71 H Polystyrene and polymethacrylate materials could be dyed with this dyestuff in strongly fluorescent orange red shades having a good fastness to light and a very good resistance to temperature.

EXAMPLE 2 l CCH2 l Ginoboom EXAMPLE 3 a. 9.5 Grams of benzothioxanthene-3,4-dicarboxylic acid hydrazide, 25.0 g of acetone-dicarboxylic acid dimethyl ester and 0.05 g of toluene-sulfonic acid were refluxed at the boil for 8 hours in ml of chlorobenzene. The organge hydrazone formed was isolated in known manner.

b. 9.2 Grams of the hydrazone obtained according to Example 3a) were heated in 46 ml of dimethyl formamide after addition of 0.09 g of anhydrous potassium sium acetate in 15 minutes at l45-l50C to give the mixture of dyestuff isomers of the formula l le-N v -(cI+Il)1lCn OCIIJ 021150 0 c c---C- o1-n ,6cn3 15 l l The orange yellow product very well soluble in aro matic solvents dyed rigid PVC in intensely fluorescent orange yellow shades having a good fastness to light and a very good thermal stability.

. The following Table lists further dyestuffs which are btained according to the methods described in the acetate for 15 minutes to 145'l50C. After cooling the mixture was diluted with methanol and the red orange dyestuff mixture of the formula lS-cmcooom c1130 oo fi :-c cmc00o1n l l T was isolated in known manner. On polyester materials 25 clear orange dyeings fast to sublimation were obtained with this dyestuff.

' EXAMPLE4 R S h D. m a X E e v 0 b 08 0 5 3 3 e 6 M m g m m rmlw r mmm m l f .mv .m w mmmammw mo mmOm gbl 001 m c W H l d .w mm m m .d n .u m eamwt lvC JP mmmx yO w o hmfl ma r .teR u w m m e i mm k g 5.w .m m7 h mm% int y cmtOd Xe 0 d g s w 6 m efll na r. .OBI mdOhvJe am C-Rl isomers Shade X (polystyrene) Orange yellow. Orange.

The yellow hydrazone which crystallized was isolated in known manner.

b. 15.0 Grams of the hydrazone obtained according 40 Example Orange red. Orange. Orange red. lied orange. Orange yellow. Orange. D0. 1

Orange yellow. Orange.

Do. 0 range red.' Orange. Orange red. Orange yellow. Orange. Orange red. Orange.

I 1 {{[II {I {I1 HIHHIHIIIIIHJIHHHII l PIHHIHIIITTIIIIHHII l IIII IIIIIAIIYL IIILYLII I lllllllllll lwl l 1 Orange red.

O Orange SSSSSSSSSSS 1 III! I [ll llllTillI [ILL-IL III HHlllll III ()Clla l-l [.ll ll lll.

an: [Ill llll 0000 0000 [I 11 Continued Shade Example R1 R2 It; R. R5 R R1 X (polystyrene) 37 0Hi COQCHH JHwHmCHQ H H H H H s Do.

-c00(oHi)n0Hg H H H H H s Do. -COO(CH2)11CH3 0 CH3 H H H H s Bluish red. OOO(CH2)15CH; H H H H H S Orange red Fol. 661

CH3 -COO(CH2}16CH3 0CH3 H H H H s Bluish red. -(cHQ)laCH3 COOO2H5 H H H H H 8 Orange red. CHECOOCH; COOCH3 -OCH3 H H H H 3 Bluish red. COOC;H5 'COOC2H5 H H H H H S Red orange. c0ocQH5 c00CtH5 OCH3 H H H H s Bluish red.

CH; H H H H H S Orange red.

CONH

47 3 COCH= H H H H H 8 Do.

48 Same 000H3 OCH; H H H H s Bluish red.

d -o0ocH, H H H H H s Orange red.

CONH2 H H H co0c2H5 H 0 Do. CO0C2H5 H H H 410001115 H s Do.

We claim: 0 (321 150 OC(l l( --Cll:i 1. Benzoxanthene or benzothioxanthene dyestuffs 11 ii i h consisting of a mixture of the compound of the formula \I 1 i i I I l l i l i O -CH3 I A II e R fi coocmi R; 1 11, 0 0

X Re I in which formulas X is oxygen or sulfur, R is hydrogen, alkyl with l to 20 carbon atoms, methoxy carbonylmethyi, ethoxycarbonylmethyl, alkoxycarbonyl with l to 4 carbon atoms or phenyl, R is alkoxycarbonyl with 1 to 20 carbon atoms, alkanoyl with 1 to 4 carbon atoms, benzoyl. cyano, carbamoyl or phenylcarbamoy], 7

3. The dyestuff consisting of the mixture of isomers of the formula 4. The dyestuff consisting of the mixture of isomers of the formula C O 0 (CH CH:

C J10 O(CIlz)11CHa 10 v 7. The dyestuff consisting of the mixture of isomers of the formula 2ll500 C-(.J' |i(lll3 l N l 8. The dyestuff consisting of the mixture of isomers 3 of the formula L CII;COOCII to l 0 li-N b o 0 cm 5. The dyestuff consisting of the mixture of isomers of the formula 6. The dyestuff consisting of the mixture of isomers of the formula 000cm \JJCCHQCO OCH:

cum-

RA /V 

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